Process for the preparation of fast dyeings or prints of synthetic fiber materials

ABSTRACT

A process for the preparation of fast dyeings or prints on synthetic fibrous materials, which comprises treating the said fibrous materials in an aqueous dispersion or in an organic solvent with dyestuffs of the formula   IN WHICH A represents alkyl of one to four carbon atoms being unsubstituted or substituted by hydroxyl, lower alkoxy, phenoxy,   OR COMBINATIONS OF TWO MEMBERS THEREOF, AND B represents phenyl being unsubstituted or substituted by fluorine, chlorine, bromine, alkyl of one to four carbon atoms, alkoxy of one to four carbon atoms, trifluoromethyl, cyano, nitro, carbo(lower)alkoxy, acetyl, benzoyl or phenyl or combinations of two or three members thereof, or naphthyl, the yellow dyeings or prints so obtained being distinguished by excellent fastness properties, particularly by a good fastness to light and the extraordinary high fastness to thermofixation.

United States Patent [1 1 Kallay et al.

221 Filed: Feb. 22, 1973 21 Appl.No.:334,835

[30] Foreign Application Priority Data Feb. 26, 1972 Germany 2209210 [52] US. Cl. 8/41 A, 8/41 R, 8/41 B, 8/41 C, 8/41 D, 8/71, 8/94, 260/193 [51] Int. Cl. D06]! 3/72, C09b 29/32 [58] Field of Search8/4l R, 41 A, 41 B, 41 C, 41 D, 8/71, 94; 260/193 [56] References Cited UNITED STATES PATENTS 3,382,228 5/1968 Ferrari et al 260/158 3,252,968 5/1966 Resnick et al. 260/193 Primary ExaminerDonald Levy Assistant Examiner-Bruce H. Hess Attorney, Agent, or FirmCurtis, Morris & Safford [451 Feb. 19, 1974 [57] ABSTRACT A process for the preparation of fast dyeings or prints on synthetic fibrous materials, which comprises treating the said fibrous materials in an aqueous dispersion or in an organic solvent with dyestuffs of the formula in which A represents alkyl of one to four carbon atoms being unsubstituted or substituted by hydroxyl, lower alkoxy, phenoxy,

or combinations of two members thereof, and B represents phenyl being unsubstituted or substituted by fluorine, chlorine, bromine, alkyl of one to four carbon atoms, alkoxy of one to four carbon atoms, trifluoromethyl, cyano, nitro, carbo(lower)a1koxy, acetyl, benzoyl or phenyl or combinations of two or three members thereof, or naphthyl, the yellow dyeings or prints so obtained being distinguished by excellent fastness properties, particularly by a good fastness to light and the extraordinary high fastness to thermofixation.

11 Claims, N0 Drawings PROCESS FOR THE PREPARATION OF FAST DYEINGS OR PRINTS OF SYNTHETIC FIBER MATERIALS The present invention relates to a process for the by means of concentrated sulfuric acid at room temperpreparation of fast dyeings or prints on synthetic fiber materials, wherein said fiber materials are treated with dye-stuffs of the general formula (1) in which A stands for an alkyl group having one to four carbon atoms, which may be substituted by a hydroxy, alkoxy, phenoxy and/or acyloxy group, and B stands for a naphthyl radical or a phenyl radical which may be substituted by a halogen atom, an alkyl and/or alkoxy group, each having one to four carbon atoms, a trifiuoromethyl, cyano, nitro, carbalkoxy, acetyl, benzoyl and/or phenyl group, the alkoxy group thereof containing one to four carbon atoms, in an aqueous dispersion or in an organic solvent.

The acyl groups mentioned may, for example, be the acetyl, propionyl and benzoyl groups.

Dyestuffs of the formula (2) in which R stands for a hydrogen atom, an alkyl group having one to four carbon atoms, or the acetyl, propiony] or benzoyl group and B is defined as above, are preferably used.

The dyestuffs may also be used in mixture with each other or with other dyestuffs.

On principle, the novel dyestuffs used according to the process of the invention are prepared in known manner by diazotizing a diazo component of the formula (3), preferably of the formula (4) for example in a solution or suspension of a mineral acid with nitrite and coupling with a coupling component of the formula (5) for example in a weakly alkaline, neutral or acid solution or suspension.

Dyestuffs of the formula (2), in which R stands for an acyl group, may be obtained by acylating dyestuffs of the formula (2), in which R stands for a hydrogen atom, in known manner with a corresponding acid or a suitable acid derivative, such as an acid chloride or anhydride.

The coupling components of the formula (5) may be prepared, for example, by particular hydrolysis of cyano-aceto-anilides of the formula (6) ature.

In the above formulae (3), (4), (5) and (6), A, B and R are defined as above.

As synthetic fiber materials, there are mentioned, for example, fibers made from cellulose esters, polyesters, polyolefins, polyamides, polyurethanes and polyacrylonitriles, preferably cellulose esters, such as cellulose acetate and cellulose triacetate; especially fibers made from polyesters, such as polyethylene terephthalate. The synthetic fiber materials may also be blended with each other or with natural fibrous materials, such as cellulose fibers or wool. These materials may furthermore be dyed or printed in various processing forms, for example as combed material, flakes, filaments, knit or woven fabrics.

The dyestuffs used according to the invention are applied, on principle in known manner, generally from an aqueous dispersion but also from an organic solvent. The dyestuffs may be dispersed, for example, by grinding them in the presence of a dispersing agent, such as a condensation product of formaldehyde and a naphthalene-sulfonic acid.

Otherwise, the dyeing conditions depend, to a large extent, on the type of synthetic fiber materials and their processing form.

For example, shaped articles made of cellulose acetate are dyed at a temperature ranging from 74 to C, whereas cellulose triacetate fibers are dyed at a temperature of from about to C.

As to a polyamide fiber material, the dyestuffs are applied at a temperature of from about 90 to 120C. Polyester fiber materials are dyed according to known methods in the presence of carriers, such as ortho or para-phenyl-phenol, methyl-naphthalene or methylsalicylate, at a temperature of about 100 to about C, or in the absence of carriers at higher temperatures, for example between 120 and C. Moreover, according to the present process, the dyestuffs may also be applied to the said fibrous materials by pad-dyeing with or without a thickening agent, for example a tragacanth thickener, and fixed under the action of heat, for example by means of vapor or dry heat over about half a minute to 30 minutes at a temperature of from about 100 to 230C. In order to improve the fastness to rubbing, the material thus dyed as then freed from dyestuff adhering to its surface, for example, by washing or subjecting it to a reductive after-treatment. This reductive after-treatment is generally performed at 60 to 120C in a liquor containing an aqueous sodium hydroxide solution, sodium dithionite and a non ionic detergent, for example an addition product of ethylene oxide and phenol.

For the dyeing of synthetic fiber materials from organic solvents, the dyestuff may, for example, be allowed to be absorbed by the fiber from the solution at room temperature or at an elevated temperature, preferably at about 70 to about 130C, where required under pressure, or a knit or woven fabric may be impregnated in a continuous operation with a dyestuff solution, dried and exposed to heat for a short time, for example at a temperature of from about 180 to about 210C.

As solvents to be used for the exhaustion method, The p f the dyebath was adjusted to 5 t0 there may, for example, be mentioned solvents which y means of ic d. ithin 30 to 60 minutes, the are not miscible with water and have boiling points of temperature was Yaled to boiling temperature and the b t 40 t b t 170C, h as li h i h l dyeing operation was carried out for 90 minutes at this t d h d b f example methylene hl id 5 temperature. The fabric was then taken out, rinsed and trichloro-ethane, trichloro-ethylene, perchloroethylene shbleeted to a reductive after treatment for 20 minutes or trifluoro-trichloro-ethane. For a continuous dyeing at to in a bath Containing, P hter, six Parts operation, there may especially be used water-miscible of sodium hydroxide Solution foul Parts 0f solvents, for example alcohols or dimethylformamide. dithiohhe and one P b a hen iohie detergent- The solvents may, of course, also be used in mixtures The y fabne was h y "heed and drledwith each other and may contain further adjuvents A yellow dyemg havlhg y good fastness Properties which are soluble in solvents, for example oxyalkylwas Obtamed, especially a g fastness g h ation products of fatty alchols, alkylphenols and fatty thermofixaheh as well as a hlgh eoler y A material acids made of cellulose acetate was dyed in the same man- For the production of prints on synthetic fiber mateh the P of the dyebath being advantageously i l f example those made f polyesters p0]yam justed to 6 to 6.5. A reductive after-treatment was, ides or cellulose triacetate, the dyestuffs to be used achowever, hot 'ycording to the invention may be applied in the form of The dyestuff of the formula could be Obtained as aqueous compositions which may contain suitable follows: thickeners and fixation-promoting agents in addition to Parts -F e'fl' y yyh fi l divided dyestuffs Fixation is performed f benezene were dissolved while hot in 400 parts of water example after printing and drying, by means of steamand 120 Parts OfSN hydrbehlbfle acid and, after having ing under atmospheric pressure or under elevated presbeen Poured 2,000 Parts of lee water, the Solulifln sure of up to 2.5 atmospheres gage over 10 to 0 i was diazotizcd with 40 parts by volume ofa 5N sodium u Fi i may l b b h about b h action nitrite solution. 45.5 parts of the coupling component f h i f about 160 to about 210C f a i d f malonic acid-amide-2-nitro-anilide were dissolved at seconds to 10 minutesv room temperature in 800 parts of water and 54 parts by The novel dyestuffs to be used according to the in- Volume of a 33 lael'eeht aqueous sodium hydroxide vention afford yellow dyeings and prints having excellube" after two Parts of a ionic emulsifier, lent fastness properties. Especially striking are the good 30 such as a reaehoh Product of O1eyl alcohol and 30 "1015 fastness to light and the extraordinary fastness to therof ethylene Oxide had been added, the solution was p fi ti cipitated while stirring in a finely divided form by Dyestuffs having a structure very much comparable quickly adding 40 Parts by Volume of glacial aeetie to that of the dyestuffs of the invention are disclosed in acid- The (hazenhhh salt solution was then added and US. Pat. No. 3,252,968 and can be used as pigments, 35 the P was adjusted l about 65 y means of 2N for example for the pigment printing. However, these sodium hydroxide solution known dyestuffs have practically no absorptive power The Precipitated dyestuff was isolated y filtration on synthetic fiber materials and are therefore comand washing- It could be dried or brought into a finely pletely useless for the dyeing and printing of said matedivided dispersion in the form of the aqueous filter resirials. Hence, it is very surprising that the dyestuffs to be 40 due sing a Commercial dispersing agent for example used according to the invention have a very good aba Condensation Product of formaldehyde and a sorptive power on synthetic fiber materials and yield haphthalehe-sulfohie acidintense dyeings and prints having very good fastness properties. EXAMPLE 2 The following examples illustrate the invention, the 10 parts of a polyester fabric were introduced into a parts and percentages being by weight unless stated dyebath heated to C and containing 400 parts of otherwise. The parts by volume are to the parts by softened water and 0.2 part of the dyestuff of the forweight as liter to kilogram under normal conditions. mula (8) NO; N0

in a finely divided form.

The pH-value of the dyebath was adjusted to 5 to 5.5 by means of ammonium sulfate and acetic acid. Within 40 to minutes, the temperature was raised to C. At this temperature, dyeing was carried out for 1 hour. mg e w- 60 The dyed material was then subjected to the after- N02 N01 treatment disclosed in Example 1 and finished.

CONHz H CH O N N JZHCO NH A yellow dyeing having excellent fastness properties HOTC T and a high color yield was obtained.

EXAMPLE 1 10 Parts of polyester yarn were introduced into a dyebath heated to 60C and containing 300 parts of softened water, 0.3 parts of a finely divided dyestuff of the formula (7) (7) Similar results were obtained using a fabric made of cellulose triacetate fibers instead of polyester fabric one part of a commercial carrier, for example oand carrying out the dyeing operation at a temperature phenyl-phenol, and 0.5 parts of ammonium sulfate. of l 10C.

- treatment disclosed in Example 1.

Dyeings having the same good fastness properties v EXAMPLE 3 A blended fabric of polyester and cellulose fibers was impregnated at to C with a dyeing liquor, the pH of which was adjusted to 5 to 5.5 by means of acetic acid and which contained 10 g per liter of the finely divided dyestuff of the formula (9) N01 or The fabric was then dried at a temperature of from 100 to l 10C. Fixationwas brought about by dry heat for 30 to 90 seconds at 190 to 230C. Finally, a reductive after-treatment as disclosed in Example 1 was made and the fabric was finished.

A yellow dyeing having excellent fastness properties, especially a very good fastness to subliming, was obtained. Similar high-quality dyeings were obtained by dyeing cellulose triacetate fiber materials in the same manner.

The dyestuff of the formula (9) was obtained using 43.5 parts of malonic acid-amide-3'-chloro-anilide as the coupling component and otherwise following the EXAMPLE 4 A polyester fabric was printed with a printing paste containing, per 1,000 parts, in addition to a commercial thickener, such as alginate and starch ether as well as further usual additives, 200 parts of an aqueous dyestuff composition containing 10 percent of the finely 10 divided dyestuff of the formula 1 l0) The dyestuff was then fixed by means of hot air for 60 seconds at 200C.

The print was rinsed, subjected to a reductive aftertreatment in a bath containing sodium dithionite and sodium hydroxide solution, then cleaned again in anlent fastness properties, especially an outstanding fastmess to thermofixation, was obtained. Similar good results were obtained by carrying out the fixation for 20 minutes by means of pressurized steam of 2 atmospheres gage.

When, instead of a polyester fabric, a fabric made of 43 cellulose triacetate fibers was used, for which no reductive after-treatment was necessary, color-intense prints having very good fastness properties were also obtained.

The dyestuff of the formula 10) was obtained by acylating the dry dyestuff of the formula (9), which could be prepared as in Example 3, with acetic acid anhydride.

EXAMPLE 5 A fabric made of polyester fibers was printed with a printing paste according to Example 4, containing, however, a dyestuff of the formula (1 l) I co-Nm mc-o-om-om-ogmN-oH-co-NHQ and then dried.

The fixation was carried out by steaming under atm0- spheric pressure for 30 minutes.

After the cleaning and drying operation, a reddish yellow print having a high color intensity and good fastr in Example 1 The following Table comprises further dyestuffs of the formula (1) to be used according to the invention.

| (|3ONH2 A0-N=NCH-OONHB (1) TABLE I Shade on EL polyester No. A B fibers Ph enyl Yellow 3-trlflu0romethyl-phenyl- D0. 2-ch10ro-4-nltro-phenyl Do. 2-chloro-phenyl D 0. B-hromo-phenyl D o. 4-fiuom-phenyl D0. CH3CO0C2H4- 2-chloro phenyl" Do. CH3COOC2H| 3-cyano-pl1enyl..- Do. 4-i-propyl-phenyl Do. Z-methyl-ph enyl Do. 4-ethoxy-pheny1. Do. a-Naphth D0. 18.-.. CH3COOC2H4 4-blphen Do. 19.... CHzOCrHr- 2-methoxyphenyl- Redidllsh e ow. CHzOCgHr- Mhloro-phenyl "Ye ow. CHz0CgH4- 4-t-butyl-phenyl. Do. CHaOCzHr- 3-acetyl-phenyl.. Do. CHrOC Hw- 4-benzoyl-phenyl Do. CzH10CzH 4-fluoro-phenyL. Do. C3H70C2H4- -carbethoxy-phenyL. Do.

26. HO-CH-CH Phenyl Do.

CH2OC5H5 27... CzH5OCzH 2-ethyl-phenyl...-. Do. 28... CzH5COOCzH;- 3-ch1orophenyl.... Do. 29.. CzH5COOCzH 2-carbobutoxy-phen Do. 30..... CaH CO0C'zH4 3-cyano-phenyl Greefiilsh ye ow. 31... CH COOC,H; 2-trifluor0methyl-pl1enyl.. Do. 32.... HOC2H4- 4-methyl-phenyl Yellow. 33.... H0C2H 4-butoxy-phenyl Reddish yellow. 0CH 3-acetyl-phenyl... Yellow 35.... HOCHzCH(OH)CHz 4-fluoro-phenyl... Do. CH:4 2-metl1yI-phenyl. Do. 37.... CH 3-ehlor0-phenyl Do. 38.... C:H1 2-bromo-phenyL- Do. G 4-t-butyI-phenyL... Do. 40..... CH.-; fl-methoxy-phenyl Reddish yellow. 41..... C H Z-carbomethoxy-phenyl... Yellow. 42.... C4Hr- 2-nltro-phenyl Do. C4Hn 2,4,5-trlchlorohenyL. D0. 44.... CzHr- 2,5dlmethyl-p enyl Do. 45..... CzH5CO0CzH4 fi-nitro-phenyl D0. 46..... CzH5COOCzH4- 4-trifluoromethyl-2-nltro- D0.

pheny]. 47.... CHzOCzH4- 2-nltro-phenyl..-. Do. a-Naphthyl D0.

We claim:

l. A process for the preparation of fast dyeings or prints on synthetic fibrousmaterials, which comprises treating the said fibrous materials in a dye bath selected from the group consisting of an aqueous dispersion, an organic solvent and mixtures thereof with a dyestuff of the formula in which A represents alkyl of one to four carbon atoms being unsubstituted or substituted by hydroxyl, lower alkoxy, phenoxy,

or combinations of two members thereof and B represents phenyl being unsubstituted or substituted by fluorine, chlorine, bromine, alkyl of one to four carbon atoms, alkoxy of one to four carbon atoms, trifluoromethyl, cyano, nitro, carbo(lower)-a lkoxy, acetyl, benzoyl or phenyl or combinations of two or three memous dispersion of the dyestuffs contains a thickening agent.

7. A process as claimed in claim 5, wherein the dyestuffs are fixed by steaming or heating them with dry heat at a temperature between about and about 230C.

8. A process as claimed in claim 1, wherein the fibrous materials are impregnated with the said dyestuffs from an organic solvent and dried, and the dyestuffs are subsequently fixed by a short-time action of heat.

9. A process as claimed in claim 1, wherein the dyestuffs are fixed by a shoft-time action of heat at a temperature of from about 180C to about 210C.

10. A process as claimed in claim 1, wherein the said fibrous materials are printed with water-containing preparations of the said dyestuffs and the dyestuffs are subsequently fixed bydrying the prints and steaming them under atmospheric pressure or elevated pressure of up to 2.5 atmospheres gage or by a short-time action of hot air of about 180 to about 210C.

1 l. A process as claimed in claim 10, wherein the water-containing preparations of the dyestuffscontain'a member selected from the group consisting of a thickening agent, a fixing accelerator and a combination thereof. 

2. A process as claimed in claim 1, wherein the synthetic fibrous material is selected from the group consisting of cellulose acetate, cellulosetriacetate, polyamides, polyurethanes, polyolefines, polyacrylonitriles and polyesters.
 3. A process as claimed in claim 1, wherein the said fibrous materials are dyed with an aqueous dispersion of the said dyestuffs at a temperature between about 75* and about 140*C in the absence or in the presence of a carrier.
 4. A process as claimed in claim 1, wherein the said fibrous materials are dyed with the said dyestuffs from organic solvents between room temperature and about 130*C.
 5. A process as claimed in claim 1, wherein the said fibrous materials are padded with an aqueous dispersion of the said dyestuffs and the dyestuffs are subsequently fixed at elevated temperature.
 6. A process as claimed in claim 5, wherein the aqueous dispersion of the dyestuffs contains a thickening agent.
 7. A process as claimed in claim 5, wherein the dyestuffs are fixed by steaming or heating them with dry heat at a temperature between about 100* and about 230*C.
 8. A process as claimed in claim 1, wherein the fibrous materials are impregnated with the said dyestuffs from an organic solvent and dried, and the dyestuffs are subsequently fixed by a short-time action of heat.
 9. A process as claimed in claim 1, wherein the dyestuffs are fixed by a short-time action of heat at a temperature of from about 180*C to about 210*C.
 10. A process as claimed in claim 1, wherein the said fibrous materials are printed with water-containing preparations of the said dyestuffs and the dyestuffs are subsequently fixed by drying the prints and steaming them under atmospherIc pressure or elevated pressure of up to 2.5 atmospheres gage or by a short-time action of hot air of about 180* to about 210*C.
 11. A process as claimed in claim 10, wherein the water-containing preparations of the dyestuffs contain a member selected from the group consisting of a thickening agent, a fixing accelerator and a combination thereof. 